CN105353015A - Preparation method and application of poly(3,4-ethylenedioxythiophene) composite film - Google Patents

Preparation method and application of poly(3,4-ethylenedioxythiophene) composite film Download PDF

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CN105353015A
CN105353015A CN201510875842.6A CN201510875842A CN105353015A CN 105353015 A CN105353015 A CN 105353015A CN 201510875842 A CN201510875842 A CN 201510875842A CN 105353015 A CN105353015 A CN 105353015A
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electrode
bsa
pedot
solution
preparation
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CN105353015B (en
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任帅斌
耿继亚
陈占飞
徐方成
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Xiamen University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10Definition of the polymer structure
    • C08G2261/11Homopolymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2489/00Characterised by the use of proteins; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films

Abstract

A preparation method and application of a poly(3,4-ethylenedioxythiophene) (PEDOT) composite film relate to the field of electrochemical sensors. The preparation method of the poly(3,4-ethylenedioxythiophene) composite film comprises the following steps: (1) respectively preparing an EDOT solution and a BSA (Bull Serum Albumin) solution; (2) mixing the EDOT solution and the BSA solution which are prepared in the step (1) to obtain a mixed solution; (3) taking a Pt electrode as a working electrode and a counter electrode and Ag/AgCl as an auxiliary electrode, using a CHI621B electrochemical workstation, and performing electrochemical scanning in the mixed solution obtained in the step (2) to obtain a poly(3,4-ethylenedioxythiophene) composite film, namely a PEDOT (BSA) composite film. The prepared PEDOT (BSA) composite film can be applied to preparation of electrode materials which comprise, but are not limited to, a platinum wire electrode, a carbon paper electrode, an Au electrode and the like.

Description

A kind of preparation method of poly-dioxyethylene thiophene composite membrane and application
Technical field
The present invention relates to electrochemical sensor, especially relate to the preparation method and the application that strengthen a kind of poly-dioxyethylene thiophene composite membrane of poly-dioxyethylene thiophene (PEDOT) membrane stability with bovine serum albumin (BSA).
Background technology
PEDOT molecular structure is simple, energy gap is little, conductivity is high, and the polymeric membrane being suitable as electrochemical sensor is modified on electrode substrate (as Pt, Au etc.).Because Pt is water wettability, and PEDOT is hydrophobicity, make the PEDOT film compatibility being aggregated in Pt surface good not, in use procedure, PEDOT film is easy to even come off from Pt sur-face peeling, affects the stability of working electrode, be unfavorable for the carrying out of testing, therefore being necessary to find a kind of easy method, for strengthening the stability of PEDOT film, maintaining the good electric conductivity of PEDOT film simultaneously.
Summary of the invention
The object of this invention is to provide a kind of cheap adulterant BSA and for improving PEDOT membrane stability, PEDOT (BSA) composite membrane after improvement by tens of times of use, can be used for preparation method and the application of a kind of poly-dioxyethylene thiophene composite membrane that target product detects in system.
The preparation method of described a kind of poly-dioxyethylene thiophene composite membrane, comprises the following steps:
(1) dioxyethylene thiophene (EDOT) solution and BSA solution is prepared respectively;
(2) the BSA solution that dioxyethylene thiophene (EDOT) solution step (1) prepared and step (1) are prepared mixes, and obtains mixed liquor;
(3) with Pt electrode for working electrode and to electrode, Ag/AgCl is auxiliary electrode, use CHI621B electrochemical workstation, Electrochemical Scanning is carried out in the mixed liquor that step (2) obtains, obtain poly-dioxyethylene thiophene composite membrane, i.e. PEDOT (BSA) composite membrane, the electrode designations obtained is PEDOT (BSA)/Pt.
In step (1), described preparation dioxyethylene thiophene (EDOT) solution can prepare dioxyethylene thiophene (EDOT) solution that volumetric molar concentration is 0.01M, is the lithium perchlorate (LiClO of 0.1M in described dioxyethylene thiophene (EDOT) solution containing volumetric molar concentration 4); Described dioxyethylene thiophene (EDOT) solution normal temperature keeps in Dark Place, Keep agitation; Described preparation BSA solution can prepare the BSA solution that mass ratio is 7.0mg/ml, 4 DEG C of Refrigerator stores.
In step (2), the volume ratio of described dioxyethylene thiophene (EDOT) solution and BSA solution can be 6: 1, and the mass concentration of the final BSA of described mixed liquor can be 1.0mg/ml.
In step (3), the specification of described Pt electrode can be φ 0.6mm × 15mm, and described auxiliary electrode can adopt Ag/AgCl (3MNaCl) to be auxiliary electrode; The scanning current potential of described Electrochemical Scanning can be 0 ~ 1V, and sweep speed can be 0.01V/s, and the scanning number of turns can be 5 circles, and operating temperature can be 25 DEG C, working electrode is polymerized length and can be 1cm.
Prepared poly-dioxyethylene thiophene composite membrane and PEDOT (BSA) composite membrane can be applied preparing in electrode material, and described electrode material includes but not limited to platinum electrode, carbon paper electrode, Au electrode etc.
Carry out in the process of testing at use PEDOT/Pt electrode, find that the PEDOT film being aggregated in Pt surface often has the phenomenon of chapping and even coming off, this may be because the adhesion condition of PEDOT film on Pt is bad, causes PEDOT slowly to come off from Pt along with time and scan action.
In standard biologic mensuration program, BSA is often used as a kind of retarding agent, is occupied the space of fixed surface by non-specific binding ability.In order to strengthen the stability of PEDOT film on Pt electrode, the present invention, when with electrochemical process polymerization PEDOT film, adds the bovine serum albumin (BSA) of 1.0mg/ml, observes BSA to the impact of PEDOT membrane stability in EDOT monomer solution.
Accompanying drawing explanation
Fig. 1 is the comparison of PEDOT/Pt and PEDOT (BSA)/Pt electrode electrical conductivity in potassium ferricyanide solution.In FIG, curve (a) is PEDOT/Pt, and curve (b) is PEDOT (BSA)/Pt.
On Fig. 2 platinum electrode, PEDOT film compares with PEDOT (BSA) membrane stability.In fig. 2, (a) is PEDOT film, and (b) is PEDOT (BSA) film.
The infrared spectrogram of Fig. 3 BSA powder and platinum plate surface PEDOT, PEDOT (BSA) film.In figure 3, curve (a) is BSA, and curve (b) is PEDOT, and curve (c) is PEDOT (BSA).
On Fig. 4 carbon paper, PEDOT film compares with PEDOT (BSA) membrane stability.In the diagram, (a) is PEDOT film, and (b) is PEDOT (BSA) film.
Embodiment
In order to be illustrated more clearly in the present invention, following examples will be described in detail the present invention by reference to the accompanying drawings.
Embodiment 1
1) by the Pt sheet of 0.5cm × 1.0cm, be immersed in BSA solution and take out after 5min.
2) in Y type cell, add 0.1MPB (pH6.2) and the 200 μ lBio-RadProteinAssay of 800 μ l, use sealed membrane cover colorimetric notch and mix.
3) the Pt sheet of taking-up is immersed in the Bio-RadProteinAssay solution prepared, leaves standstill 5min at 25 DEG C, and compare with blank sample.
Result shows, solution colour obviously becomes blue, describes BSA and has good compatibility at Pt electrode surface, can as improving the additive of PEDOT in Pt surface affinity.
Embodiment 2
1) get the EDOT solution 6ml of 0.01M, fully mix with the BSA solution of the 7mg/ml of 1ml, the concentration making final BSA is 1.0mg/ml, and mixed liquor is labeled as A;
2) get the EDOT solution 6ml of 0.01M, fully mix with the deionized water of 1ml, make EDOT concentration and step 1 in mixed liquor) in identical, mixed liquor is labeled as B;
3) respectively with PEDOT/Pt and PEDOT (BSA)/Pt for working electrode, Pt is to electrode, and Ag/AgCl (3MNaCl) is auxiliary electrode, with the K of 0.01M 3[Fe (CN) 6] solution detects the response current size of Different electrodes, and make comparisons.
The electrical conductivity of PEDOT film affects the size of electrochemical sensor response current, is therefore necessary that the interpolation probing into BSA is on the impact of PEDOT film electrical conductivity.As can be seen from Figure 1, after bovine serum albumin adds, compared with the electrical conductivity of PEDOT/Pt electrode, the electrical conductivity of PEDOT (BSA)/Pt electrode reduces slightly, but still very high.
Embodiment 3
1) step and method in embodiment 1 is utilized to obtain PEDOT/Pt and PEDOT (BSA)/Pt two electrodes;
2) take PEDOT/Pt as working electrode, Pt is to electrode, and Ag/AgCl (3MNaCl) is auxiliary electrode, scans the superoxol of 1.0mM, and the scanning number of turns 10 is enclosed, scanning voltage-0.2 ~ 0.8V, sweep velocity 50mV; Repeatedly scan 5 times;
3) again with PEDOT (BSA)/Pt for working electrode, Pt is to electrode, and Ag/AgCl (3MNaCl) is auxiliary electrode, the superoxol of 1.0mM is scanned, the scanning number of turns 10 is enclosed, scanning voltage-0.2 ~ 0.8V, sweep velocity 50mV; Repeatedly scan 20 times;
4) by step 2) with 3) in used electrode deionized water fully rinse, be then placed in drying box deoxygenation and preserve, make it fully dry;
5) by step 4) in two electrode SEM observe under the enlargement factor of X100, obtain electrode surface form.
Obtain result as shown in Figure 2.
Because Pt electrode surface is more hydrophilic, the oligomer of EDOT and PEDOT are then quite hydrophobic in aqueous, and this makes PEDOT film can not stably be attached to Pt electrode surface.Therefore we wish that the interpolation of BSA can change the hydrophilic and hydrophobic on Pt surface, thus PEDOT is more compacted be attached to Pt surface.
PEDOT/Pt electrode and PEDOT (the BSA)/Pt electrode SEM image (enlargement factor X100) after using certain number of times can be seen respectively by Fig. 2, wherein: figure (a) is the image of PEDOT/Pt electrode after using for several times, and many crackles have obviously appearred in film surface; And to scheme (b) be that PEDOT (BSA)/Pt electrode uses the image after more than 20 times, PEDOT (BSA) film surface still flat smooth can be seen, show good stability.
Embodiment 4
In order to understand the interpolation of BSA to the impact of PEDOT membrane structure, FTIR analysis is carried out to BSA powder and PEDOT/Pt, PEDOT (BSA)/Pt electrode.
Preparation of samples process:
(1) select the base material of Pt plate as polymeric membrane of 0.5cm × 1.0cm, increase surface area.
(2) by three-electrode system, with Pt plate for working electrode, Pt silk is to electrode, and Ag/AgCl (3MNaCl) is contrast electrode, by method polymerization PEDOT and PEDOT (BSA) of CV scanning.Scanning current potential is 0.0 ~ 1.0V, and sweep speed is 0.01V/s, and the scanning number of turns is 40 circles, and temperature is 25 DEG C, and polymerized area is 0.5cm × 0.5cm.Obtained PEDOT film one respectively, PEDOT (BSA) film one.
(3) sample test is carried out with reflective FTIR.
In test process, each sample need diverse location repeated measurement 4 times, to ensure data accuracy.
The characteristic peak positions of contrast PEDOT film can find, PEDOT (BSA) composite membrane not only has the feature crest of PEDOT film, has the feature crest of BSA simultaneously; And adding of BSA makes all PEDOT characteristic peak positions all increase, to offseting; Consider the electrochemistry formated mode of this electrode, can learn that adding of BSA makes the one-piece construction of PEDOT there occurs change, be that is have between chemical bond interactional between BSA and PEDOT, having more than is simple contact.
The infrared spectrogram of BSA powder and platinum plate surface PEDOT, PEDOT (BSA) film is see Fig. 3.
Embodiment 5
1) get the EDOT solution 6ml of 0.01M, fully mix with the BSA solution of the 7mg/ml of 1ml, the concentration making final BSA is 1.0mg/ml, and mixed liquor is labeled as A;
2) get the EDOT solution 6ml of 0.01M, fully mix with the deionized water of 1ml, make EDOT concentration and step 1 in mixed liquor) in identical, mixed liquor is labeled as B;
3) with carbon paper (CP, specification is) be working electrode, Pt is that Ag/AgCl (3MNaCl) is auxiliary electrode to electrode (specification is φ 0.6mm × 15mm), use CHI621B electrochemical workstation, in solution A, carry out Electrochemical Scanning.Scanning current potential is 0.0 ~ 1.0V, and sweep speed is 0.01V/s, and the scanning number of turns 5 is enclosed, and operating temperature is 25 DEG C, and working electrode being polymerized length is 1cm.Then, use the same method and carry out electrochemical polymerization in solution B.Working electrode after two polymerizations is labeled as PEDOT/CP and PEDOT (BSA)/CP respectively.
4) take PEDOT/CP as working electrode, Pt is to electrode, and Ag/AgCl (3MNaCl) is auxiliary electrode, scans the superoxol of 1.0mM, and the scanning number of turns 10 is enclosed, scanning voltage-0.2 ~ 0.8V, sweep velocity 50mV; Repeatedly scan 5 times;
5) again with PEDOT (BSA)/CP for working electrode, Pt is to electrode, and Ag/AgCl (3MNaCl) is auxiliary electrode, the superoxol of 1.0mM is scanned, the scanning number of turns 10 is enclosed, scanning voltage-0.2 ~ 0.8V, sweep velocity 50mV; Repeatedly scan 20 times;
6) by step 4) with 5) in used electrode deionized water fully rinse, be then placed in drying box deoxygenation and preserve, make it fully dry;
7) by step 6) in two electrode SEM observe under the enlargement factor of X100, obtain electrode surface form.
Obtain result as shown in Figure 4, in the diagram, (a) is the image of PEDOT/CP electrode after using for several times, and many crackles have obviously appearred in film surface; And (b) to be PEDOT (BSA)/CP electrode use the image after more than 20 times, can see and show good stability by PEDOT (BSA) film surface still flat smooth.
This carbon paper through PEDOT (BSA) film modified mistake can as the working electrode in microbiological fuel cell (MFC), and test is adsorbed on the electrogenesis situation of electrode surface bacterium.

Claims (8)

1. a preparation method for poly-dioxyethylene thiophene composite membrane, is characterized in that comprising the following steps:
(1) dioxyethylene thiophene solution and BSA solution is prepared respectively;
(2) the BSA solution that dioxyethylene thiophene solution step (1) prepared and step (1) are prepared mixes, and obtains mixed liquor;
(3) with Pt electrode for working electrode and to electrode, Ag/AgCl is auxiliary electrode, use CHI621B electrochemical workstation, Electrochemical Scanning is carried out in the mixed liquor of step (2), obtain poly-dioxyethylene thiophene composite membrane, i.e. PEDOT (BSA) composite membrane, the electrode designations obtained is PEDOT (BSA)/Pt.
2. the preparation method of a kind of poly-dioxyethylene thiophene composite membrane as claimed in claim 1, it is characterized in that in step (1), described preparation dioxyethylene thiophene solution is the dioxyethylene thiophene solution of preparation 0.01M, and containing volumetric molar concentration in described dioxyethylene thiophene solution is the lithium perchlorate of 0.1M; Described preparation BSA solution prepares the BSA solution that mass ratio is 7.0mg/ml.
3. the preparation method of a kind of poly-dioxyethylene thiophene composite membrane as claimed in claim 1, it is characterized in that in step (2), the volume ratio of described dioxyethylene thiophene solution and BSA solution is 6: 1, and the mass concentration of the final BSA of described mixed liquor is 1.0mg/ml.
4. the preparation method of a kind of poly-dioxyethylene thiophene composite membrane as claimed in claim 1, it is characterized in that in step (3), the specification of described Pt electrode is φ 0.6mm × 15mm.
5. the preparation method of a kind of poly-dioxyethylene thiophene composite membrane as claimed in claim 1, is characterized in that in step (3), and described auxiliary electrode adopts Ag/AgCl (3MNaCl) to be auxiliary electrode.
6. the preparation method of a kind of poly-dioxyethylene thiophene composite membrane as claimed in claim 1, it is characterized in that in step (3), the scanning current potential of described Electrochemical Scanning is 0 ~ 1V, sweep speed is 0.01V/s, the scanning number of turns is 5 circles, operating temperature is 25 DEG C, and working electrode being polymerized length is 1cm.
7. the one that according to any one of claim 1 ~ 6 prepared by method is gathered dioxyethylene thiophene composite membrane preparing in electrode material and is applied.
8. apply as claimed in claim 7, it is characterized in that described electrode material includes but not limited to platinum electrode, carbon paper electrode, Au electrode.
CN201510875842.6A 2015-12-02 2015-12-02 A kind of preparation method and application of poly- dioxyethylene thiophene composite membrane Expired - Fee Related CN105353015B (en)

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